KR20190065490A - Phenol resin foam and method for producing same - Google Patents

Abstract

An object of the present invention is to provide a phenolic resin foam which has a low load on the environment, a high compressive strength, and is excellent in handling and fixing cost at the time of construction, and a method for producing the same. The phenolic resin foam of the present invention contains at least one member selected from the group consisting of chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins and halogenated hydrocarbons and has a density of 20 kg / m 3 or more and 100 kg / m 3 or less, Wherein the closed cell ratio is 80% or more and 99% or less, and the 10% compressive strength and the density satisfy the following formula. C? 0.5X? 7 where C represents the 10% compressive strength (N / cm2) and X represents the density (kg / m3)

Description

PHENOL RESIN FOAM AND METHOD FOR PRODUCING SAME

The present invention relates to a phenolic resin foam and a manufacturing method thereof.

In recent years, improvements in air-tightness performance and insulation performance of houses have been demanded due to improvements in consciousness of energy saving and the obligation of the next generation energy saving standards. It is expected that the thickness of the heat insulating material required will increase with the demand for improving the air-tightness performance and the heat insulating performance of such a house. However, There has been a problem that a design change is required.

As a heat insulating material for housing, there is known a heat insulating material such as glass wool, rock wool, and the like, and a foamed plastic heat insulating material obtained by foaming a styrene resin, a urethane resin, and a phenol resin. Among them, the phenol resin foam is a heat insulating material for housing which has low gas permeability and does not change its heat insulating performance over a long period of time. It is also known that the heat insulating performance of the phenolic resin foam is greatly affected by the type and state of the compound contained in the foam.

Conventionally, chlorofluorocarbons (CFCs) having a low thermal conductivity have been used as the above-mentioned compounds used in phenolic resin foams. However, CFCs have been abolished by the Montreal Protocol adopted in 1987 because they contribute significantly to ozone depletion and climate variability. As a result, the compound was converted into hydrofluorocarbon (HFC) or the like having relatively low ozone destruction coefficient. However, since it still has a high global warming coefficient, a compound having low thermal conductivity, low ozone depletion coefficient, and low global warming coefficient like CFC or HFC has been desired.

Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4 disclose chlorinated or non-chlorinated hydrofluoroolefin as a compound having a low ozone destruction coefficient, low global warming coefficient, and flame retardancy.

Japanese Published Patent Publication No. 2010-522819 Japanese Laid-Open Patent Publication No. 2013-064139 Japanese Laid-Open Patent Publication No. 2011-504538 Japanese Patent Application Laid-Open No. 2007-070507

Many chlorinated or non-chlorinated hydrofluoroolefins have been disclosed in Patent Documents 1, 2, 3, and 4, among which 1-chloro-3,3,3-trifluoropropene, 1,3,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene, 1,1,1,4,4,4-hexafluoro- It is described that 2-butene has a low ozone depletion coefficient and global warming coefficient and can be used for a foamed plastic heat insulating material. However, since these compounds have a low ozone destruction coefficient and a high warming coefficient, they have a high polarity. Therefore, when they are used for a phenolic resin foam, the phenol resin having a hydroxyl group as a hydrophilic group is plasticized to lower the compressive strength and the closed cell ratio There was a challenge. For this reason, when the conventional technology of phenol resin foam using a hydrocarbon is simply replaced with the chlorinated or non-chlorinated hydrofluoroolefin, there is a case where the foam becomes a coarse foam having a low compression strength and a low independent foam ratio . On the other hand, in the prior art, in order to increase the compressive strength, it is necessary to increase the density of the phenolic resin foam, so that the weight is increased and the handling property at the time of construction is deteriorated and the phenol resin foam is produced by using other members or spheres There is a case that a problem such as an increase in cost due to fixation occurs.

Accordingly, the present invention provides a phenolic resin foam having a low load on the environment (low ozone depletion potential and low warming coefficient), high compressive strength, and excellent handling and fixing cost at the time of construction, and a production method thereof .

DISCLOSURE OF THE INVENTION As a result of intensive studies to attain the above object, the inventors of the present invention have found that by using a specific compound and setting the density, closed cell ratio and 10% compression strength within a specific range, the load on the environment is low, , And a phenolic resin foam excellent in handling and fixing cost at the time of construction can be obtained, thereby completing the present invention.

That is, the present invention provides a process for producing a polyurethane foam which comprises at least one member selected from the group consisting of chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins and halogenated hydrocarbons, has a density of 20 kg / m 3 or more and 100 kg / Wherein the ratio is 80% or more and 99% or less, and the density of 10% compression strength and the density satisfy the following formula.

C ≥ 0.5X - 7

(Wherein C represents 10% compressive strength (N / cm2) and X represents density (kg / m3)

At least one selected from the group consisting of the chlorinated hydrofluoroolefin and the non-chlorinated hydrofluoroolefin, and the halogenated hydrocarbon.

At least one species selected from the group consisting of the chlorinated hydrofluoroolefin and the non-chlorinated hydrofluoroolefin is 1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3- Trifluoropropene, 1,3,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene and 1,1,1,4,4, Hexafluoro-2-butene, and 4-hexafluoro-2-butene.

It is preferred that the halogenated hydrocarbon is isopropyl chloride.

In addition, it is preferable to contain hydrocarbons having 6 or less carbon atoms.

Wherein the content of the at least one selected from chlorinated hydrofluoroolefins, chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins and halogenated hydrocarbons is at least one selected from the group consisting of the chlorinated hydrofluoroolefins, the non-chlorinated hydrofluoroolefins, the halogenated hydrocarbons and the hydrocarbons Is preferably 30 mass% or more.

Further, it is preferable to contain a nitrogen-containing compound.

It is preferable that the nitrogen-containing compound is a compound selected from the group consisting of urea, melamine, nuclidine, pyridine, hexamethylenetetramine, and mixtures thereof.

It is preferable that the absolute value of the dimensional change amount after 3 cycles of dry and wet repetition is 2.0 mm or less in the phenolic resin foam.

It is preferable that the phenol resin foam has a brittleness of 50% or less as determined in accordance with JIS A 9511 (2003) 5.1.4.

The present invention also provides a phenol resin foam laminate having a face material on the first and second faces of the phenol resin foam, wherein the face material is all gas permeable, to provide.

The present invention also provides a foamable phenolic resin composition comprising, on a face plate, a phenolic resin, a surfactant, a curing catalyst, and a foamable phenol resin composition containing at least one member selected from the group consisting of chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins and halogenated hydrocarbons A process for producing a phenol resin foam which is foamed and cured, characterized in that the phenol resin obtained by gel permeation chromatography has a weight average molecular weight Mw of 400 or more and 3000 or less and a viscosity at 40 占 폚 of 1000 mPa 占 퐏 (1 / min) or more and 0.5 (1 / min) or less, and the density of the phenolic resin foam is 20 kg / m 3 or more and 100 kg / m 3 or less , The closed cell ratio of the phenolic resin foam is 80% or more and 99% or less, and the 10% compressive strength of the phenolic resin foam and the Characterized in that the density of the knol resin foam satisfies the following formula: < EMI ID = 1.0 >

C ≥ 0.5X - 7

(Wherein C represents 10% compressive strength (N / cm2) and X represents density (kg / m3)

The loss tangent tan? Of the phenol resin at 40 占 폚 is preferably 0.5 or more and 40.0 or less, and the loss tangent tan? At 60 占 폚 is preferably 2.0 or more and 90.0 or less.

Since the phenolic resin foam of the present invention has the above-described constitution, the load on the environment is low, the compression strength is high, and the handling and fixing cost at the time of construction are excellent.

According to the method for producing the phenolic resin foam of the present invention, the phenolic resin foam of the present invention having the above-described constitution can be easily produced.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as " present embodiment ") will be described in detail. The present invention is not limited to the following embodiments.

The phenolic resin foam of the present embodiment contains at least one member selected from the group consisting of chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins and halogenated hydrocarbons, and has a density of 20 kg / m 3 or more and 100 kg / m 3 or less , The closed cell ratio is 80% or more and 99% or less, and the 10% compressive strength and the density satisfy the following formula.

C ≥ 0.5X - 7

(Wherein C represents 10% compressive strength (N / cm2) and X represents density (kg / m3)

In the present specification, at least one compound or mixture selected from the group consisting of chlorinated hydrofluoroolefin, non-chlorinated hydrofluoroolefin and halogenated hydrocarbon is sometimes referred to as " compound a ".

Here, since the compound? Contained in the phenol resin foam of the present embodiment has a low ozone destruction coefficient and global warming coefficient, the phenol resin foam of the present embodiment has a low environmental load.

The chlorinated hydrofluoroolefin or the non-chlorinated hydrofluoroolefin is not particularly limited, but from the viewpoint of low thermal conductivity and foamability, 1-chloro-3,3,3-trifluoropropene, 2-chloro 3,3,3-trifluoropropene, 1,3,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene, 1,1 , 1,4,4,4-hexafluoro-2-butene, and the like.

The halogenated hydrocarbon is not particularly limited, but a halogenated hydrocarbon containing at least one hydrogen element and a halogenated hydrocarbon containing at least two halogen atoms are preferable from the viewpoint of low thermal conductivity, low ozone destruction coefficient and warming coefficient, Halogenated hydrocarbons or halogenated hydrocarbons containing no fluorine atom are preferable, and isopropyl chloride is more preferable.

The compound? May contain one kind of compound selected from the group consisting of chlorinated hydrofluoroolefin, non-chlorinated hydrofluoroolefin and halogenated hydrocarbon, or may contain a plurality of compounds in combination.

The phenolic resin foam of the present embodiment may further contain a hydrocarbon, carbon dioxide, or the like (preferably, a hydrocarbon).

The hydrocarbon includes, for example, hydrocarbons having 6 or less carbon atoms. That is, the phenolic resin foam of the present embodiment may contain at least one compound selected from the group consisting of chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins and halogenated hydrocarbons, as well as hydrocarbons having 6 or less carbon atoms May be contained. Specific examples of the hydrocarbon having 6 or less carbon atoms include normal butane, isobutane, cyclobutane, normal pentane, isopentane, cyclopentane, neopentane, n-hexane, isohexane, 2,2- -Dimethylbutane, cyclohexane, and the like. Of these, pentanes such as normal pentane, isopentane, cyclopentane and neopentane, and butanes of normal butane, isobutane and cyclobutane are preferably used. These hydrocarbons may be used alone or in combination of two or more.

The phenol resin foam of the present embodiment is not particularly limited and may contain, for example, a single compound consisting of one kind of the above-mentioned compound a or plural kinds of the above-mentioned compound a or at least one kind of the above- And may contain at least one kind of the above-mentioned hydrocarbons. Among them, the phenol resin foam of the present embodiment preferably contains at least one kind of compound selected from the group consisting of chlorinated hydrofluoroolefin and non-chlorinated hydrofluoroolefin and halogenated hydrocarbon. From the viewpoint that a foam having a small average cell diameter and a high independent foam ratio and a high compression strength can be obtained, the phenol resin foam of the present embodiment can be obtained, for example, by mixing at least one kind of the above- (In particular, it is preferable to contain one or two of the above-mentioned compounds? As the first component and the hydrocarbon (pentane such as cyclopentane, isopentane and the like) as the second component.

When the phenol resin foam of the present embodiment contains a hydrocarbon having 6 or less carbon atoms, the content of the compound? Is not particularly limited, but from the viewpoint that the average cell diameter is small, the closed cell ratio is high and the thermal conductivity is low Is preferably 30 mass% or more (for example, 30 mass% or more and 100 mass% or less) with respect to the total amount (100 mass%) of the compound? And the hydrocarbon having 6 or less carbon atoms, More preferably not less than 40 mass% and not more than 100 mass%, still more preferably not less than 50 mass% nor more than 100 mass%, particularly preferably not less than 60 mass% nor more than 100 mass%, particularly preferably not less than 70 mass% nor more than 100 mass% Is not less than 80 mass% and not more than 100 mass%.

In the present embodiment, a nitrogen-containing compound may be added to the phenol resin as a formaldehyde capturing agent for reducing the amount of formaldehyde dissipated from the phenol resin foam or for imparting flexibility to the phenol resin foam.

As the nitrogen-containing compound, for example, a compound selected from the group consisting of urea, melamine, nuclidine, pyridine, hexamethylenetetramine, and a mixture thereof may be used, and urea is preferably used. Examples of additives other than nitrogen-containing compounds include nitrogen, helium, argon, metal oxides, metal hydroxides, metal carbonates, talc, kaolin, silica powder, silica, mica, calcium silicate powder, wollastonite, Fly ash, silica fume, graphite, aluminum powder and the like may be added. Examples of the metal oxide include calcium oxide, magnesium oxide, aluminum oxide and zinc oxide; metal hydroxides include aluminum hydroxide, magnesium hydroxide and calcium hydroxide; metal carbonates include calcium carbonate, magnesium carbonate, barium carbonate and zinc carbonate have. Silane-based compounds and siloxane-based compounds may also be added as additives other than nitrogen-containing compounds. These may be used alone or in combination. As the silane compound, hexamethyldisilazane, dimethoxydimethylsilane, or the like may be used. As the siloxane compound, hexamethyldisiloxane or the like may be used. Since the silane compound and the siloxane compound have non-polarity, they do not mix well with a phenol resin having a polarity. Therefore, since many bubble nuclei are formed, a foam having a small bubble diameter and a high independent bubble ratio can be obtained. The nitrogen-containing compound and the additives other than the nitrogen-containing compound may be used alone or in combination of two or more.

The density of the phenolic resin foam in the present embodiment is 20 kg / m 3 or more and 100 kg / m 3 or less, preferably 20 kg / m 3 or more and 70 kg / m 3 or less, more preferably 20 kg / M 3 or less, more preferably 22 kg / m 3 or more and 35 kg / m 3 or less, and most preferably 23 kg / m 3 or more and 28 kg / m 3 or less. When the density is lower than 20 kg / m 3, the foam film is thin, so that the foam film tends to be torn at the time of foaming, so that it becomes difficult to obtain a high independent foam structure and the compression strength is extremely lowered. If the density is higher than 100 kg / m < 3 >, the thermal conductivity of the solids derived from the solid component including the resin increases, and the heat insulating performance deteriorates.

The density refers to a value measured by the method described in " (2) Foam density of later " (evaluation). The density can be adjusted by, for example, the ratio of the compound a or the hydrocarbon, the ratio of the curing catalyst, the foaming temperature, the molecular weight of the phenol resin, the reaction rate, the viscosity of the phenol resin,

The inventors of the present invention found that when the hydrocarbon in the conventional hydrocarbon-containing phenol resin foam is simply replaced with the compound a, the viscosity increase due to the curing reaction of the phenol resin in the foam hardening step of the phenol resin foam, It is disappeared by the high compatibility with the resin, and the growth rate of the bubble is relatively increased. Therefore, it has been found that it is difficult to obtain a phenolic resin foam having a high compressive strength and excellent handling and fixing cost at the time of construction, only by replacing the hydrocarbon with the compound [alpha]. As a result of intensive studies, it has been found that the cause of this is related to the fact that the closed cell ratio and the compressive strength become excessively high or excessively low.

The present inventors have also found that by using a phenol resin having a specific range of Mw, viscosity, viscosity increasing rate constant and tan delta, it is possible to set the physical property values such as the closed cell ratio and the compressive strength to a specific range, , A phenolic resin foam having a high compressive strength and excellent handling and fixing cost at the time of construction can be obtained.

The closed cell ratio of the phenolic resin foam in the present embodiment is 80% or more and 99% or less, preferably 85% or more and 99% or less, more preferably 88% or more and 99% or less, Is particularly preferable. If the independent bubble ratio is too low, the hydrocarbons and the compound a contained in the bubble are liable to be displaced with air, so that the heat insulating performance after a long period of time deteriorates or the bubble film tends to be easily torn, .

The above-mentioned independent bubble ratio refers to a value measured by the method described in (3) Independent Bubble Ratio of (Evaluation) to be described later. The closed cell ratio can be adjusted, for example, by the viscosity of the phenol resin, the type and ratio of the compound? And the hydrocarbon, the curing condition, the oven temperature at the time of foaming and the like.

The 10% compression strength of the phenolic resin foam in the present embodiment is not particularly limited, but it is preferable that the strength of the phenol resin foam and the density of the phenol resin foam are not excessively increased (the weight is not excessively increased, Not more than 50 N / cm 2, more preferably not less than 10 N / cm 2, not more than 40 N / cm 2, more preferably not less than 6 N / N / cm2, particularly preferably not less than 12 N / cm2 and not more than 40 N / cm2, and most preferably not less than 15 N / cm2 and not more than 40 N / cm2.

The 10% compressive strength refers to a value measured by the method described in (4) 10% compressive strength, which will be described later. The 10% compressive strength may be determined by, for example, the molecular weight, the viscosity, the reaction rate of the phenol resin, the type and ratio of the compound a and the hydrocarbon, the curing conditions (for example, (For example, oven temperature), the structure of the foam (a structure having no holes in the foam film, etc.), and the like.

The phenolic resin foam of the present embodiment satisfies the above-mentioned 10% compressive strength and the density of the following formula from the viewpoints of strength against compression, handling at the time of construction, and cost reduction in fixing.

C ≥ 0.5X - 7

(Wherein C represents the 10% compressive strength (N / cm2) and X represents the density (kg / m3)

Among them, the left side C of the above formula is preferably 0.5 or more larger than the right side (0.5X - 7) from the viewpoint of the strength against compression, the handling at the time of construction, and the cost reduction during fixing. More preferably at least 0.8, more preferably at least 1.0, and particularly preferably at least 1.5.

When the density satisfies the above relationship and the density is 20 kg / m < 3 > or more, the strength of the foam is excellent, and the phenol resin foam can be used as a foamed product in a construction in which the foamed phenol resin foam is applied to a floor surface or a flat roof. There is hardly a problem that the surface becomes flaky or cracks when the user strolls upside down during maintenance.

The absolute value (the absolute value of the dimensional change) of the phenolic resin foam after 3 cycles of dry and wet repetition is preferably 2.0 mm or less, more preferably 1.6 mm or less, still more preferably 1.3 mm Or less, and most preferably 1.0 mm or less. If the absolute value of the dimensional change amount is larger than 2.0 mm, if the foamed phenol resin is shrunk by repeated dry / wet after the application of the phenol resin foam, a gap is formed at the joint portion of the foamed insulation board, Which is undesirable. On the other hand, when the phenol resin foam expands, the joint portion of the board is lifted up, so that the smoothness of the wall surface is impaired and the appearance is deteriorated.

The absolute value of the dimensional change amount is a value measured by the method described in "(5) Absolute value of dimensional change after three cycles of dry and wet repetition" of (Evaluation) described later. The absolute value of the dimensional change amount is determined by, for example, the molecular weight or the reaction rate of the phenol resin, the type and ratio of the compound? And the hydrocarbon, the amount of the curing catalyst added, the curing time of the phenol resin, Can be adjusted.

The brittleness of the phenolic resin foam in the present embodiment is preferably 50% or less, more preferably 40% or less, further preferably 30% or less, particularly preferably 20% or less, particularly preferably 15% Or less, and most preferably 10% or less. If the embrittlement is larger than 50%, the production cost is not preferable. Further, when a board made of a phenol resin foam is processed at the time of construction, the foam tends to be easily broken, which is not preferable.

The brittleness refers to a value measured by the method described in "(6) brittleness" of (Evaluation) to be described later. The brittleness can be controlled by, for example, the composition or proportion of the phenol resin, the presence or absence of additives such as nitrogen-containing compounds and plasticizers, the density of the phenol resin foam, and the crosslinking density of the phenol resin in the phenol resin foam.

The phenol resin foam in the present embodiment is obtained by foaming and curing a foamable phenol resin composition containing, for example, a phenol resin and a compound? (Preferably, a phenol resin, a surfactant, a curing catalyst, . The foamable phenolic resin composition may further contain hydrocarbons and may contain additives such as nitrogen-containing compounds, plasticizers, flame retardants, curing auxiliaries, silane compounds, and siloxane compounds. In order to control the foaming and curing rate more accurately, a plasticizer such as phthalic acid ester may be added.

The method for producing a phenolic resin foam of the present embodiment is a method for producing a phenolic resin foam which foam and cure a foamable phenolic resin composition containing a phenol resin, a surfactant, a curing catalyst and a compound on a face material, Wherein the phenolic resin has a weight average molecular weight Mw of 400 or more and 3000 or less and a viscosity at 40 占 폚 of 1000 mPa 占 퐏 or more and 100000 mPa 占 퐏 or less, (1 / min) to 0.5 (1 / min) or less.

The phenolic resin is obtained, for example, by polymerizing a compound having a phenyl group and a compound having an aldehyde group or a derivative thereof as a raw material by heating with an alkali catalyst at a temperature in the range of 40 占 폚 to 100 占 폚.

Examples of the compound having a phenyl group used for preparing the phenolic resin include phenol, resorcinol, catechol, o-, m- or p-cresol, xylenols, ethylphenols, p- Phenol and the like. Among them, phenol, o-, m- or p-cresol is preferable, and phenol is most preferable. As the compound having a phenyl group, a compound having a phenyl group of two nuclei can also be used. These phenyl group-containing compounds may be used singly or in combination of two or more.

When a compound having two or more kinds of phenyl groups is used, the "molar amount of the compound having a phenyl group" is the sum of the molar amounts of the compounds having each phenyl group to be used. When a compound having a biphenyl nucleus is used, the value obtained by multiplying the number of moles of the compound having a biphenyl nucleus by 2 is used as the molar amount of the compound having a biphenyl nucleus, Molar amount "

Examples of the aldehyde group-containing compound or derivative thereof used in the preparation of the phenol resin include formaldehyde, paraformaldehyde, 1,3,5-trioxane, tetraoxymethylene, and the like. Among them, formaldehyde and paraformaldehyde are preferable. These aldehyde-containing compounds or derivatives thereof may be used alone or in combination of two or more.

When a compound having two or more kinds of aldehyde groups or a derivative thereof is used, the "molar amount of the compound having an aldehyde group or its derivative" is the sum of the molar amounts of the compound having each aldehyde group or its derivative to be used. The "molar amount of the compound having an aldehyde group or its derivative" in the case of using paraformaldehyde is calculated by using the value obtained by dividing the weight of the paraformaldehyde used by 30 and adding 1,3,5-trioxane The "molar amount of the compound having an aldehyde group or its derivative" when used is calculated by multiplying the number of moles of 1,3,5-trioxane used by 3 by 3, and when " Molar amount of the compound having an aldehyde group or its derivative "is calculated by multiplying the number of moles of tetraoxymethylene used by 4 by the value obtained by multiplying.

The molar ratio (the molar amount of the compound having an aldehyde group or the molar amount of the derivative / the molar amount of the compound having a phenyl group) of the compound having the aldehyde group or the derivative thereof to the compound having the phenyl group used in the preparation of the phenol resin is preferably 1.5 Or more and 3 or less, more preferably 1.6 or more and 2.7 or less, further preferably 1.7 or more and 2.5 or less, and most preferably 1.8 or more and 2.2 or less. When the molar ratio of the compound having an aldehyde group to the compound having a phenyl group or a derivative thereof is 1.5 or more, the strength of the phenolic resin foam can be maintained by suppressing the decrease of the strength of the foam film at the time of foaming. In addition, since the amount of the compound having an aldehyde group required for crosslinking the phenol nuclei or the derivative thereof is satisfied and the crosslinking can be sufficiently carried out, the strength of the cell membrane of the phenolic resin foam can be increased and the improvement of the self-supporting ratio can be achieved. When the molar ratio of the compound having an aldehyde group to the compound having a phenyl group or a derivative thereof is 3 or less, the phenol resin can be easily crosslinked, the strength of the foam film of the phenol resin foam can be increased, and the improvement of the self-supporting ratio can be achieved.

The phenol resin may have a weight average molecular weight Mw determined by gel permeation chromatography by a method described in "(7) Phenol resin weight average molecular weight Mw" described later (evaluation), for example, 400 or more More preferably not less than 500 and not more than 3,000, further preferably not less than 700 and not more than 3,000, particularly preferably not less than 1,000 and not more than 2,700, and most preferably not less than 1,500 and not more than 2,500. If the weight-average molecular weight Mw is less than 400, a large amount of additional reaction sites remain in the phenol nucleus, so that the amount of heat generated after the curing catalyst is mixed with the phenol resin becomes large. Therefore, chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins and halogenated hydrocarbons The phenol resin which is plasticized by the at least one kind selected from the group consisting of the above-mentioned group is heated to a higher temperature and the viscosity is further lowered. As a result, foaming of the bubbles is caused at the time of foaming, and the closed cell ratio is lowered, so that the compression strength is lowered. In addition, if the weight average molecular weight Mw is not sufficiently large, sufficient stretching is not applied to the foamed film when the phenolic resin is foamed, so that the compressive strength tends to be lowered. Further, as described above, since the viscosity of the phenol resin is lowered, the coalescence of bubbles tends to occur at the time of curing of the foam, resulting in a lot of voids and a coarse foam having a large average cell diameter. When the weight average molecular weight Mw is more than 3000, the viscosity of the phenol resin becomes too high, and it is not preferable to obtain the required expansion ratio. In addition, since a low molecular weight component in the phenol resin is reduced, the amount of heat generated upon curing of the phenol resin is lowered, so that a sufficient curing reaction does not proceed and the compressive strength may be lowered.

The viscosity of the phenol resin at 40 占 폚 is preferably 1000 mPa 占 퐏 or more and 100000 mPa 占 퐏 or less, for example. From the viewpoint of the improvement of the independent cell ratio and the reduction of the average cell diameter, it is more preferably from 5000 mPa s to 50000 mPa 보다, and particularly preferably from 7000 mPa s to 30000 mPa 이하. If the viscosity of the phenol resin is too low (for example, less than 5000 mPa · s), the bubble nuclei in the phenol resin tends to become unstable at the time of the foaming curing, so that the cell diameter tends to become excessively large. Further, the foaming film tends to be easily torn by the foaming pressure, which tends to result in deterioration of the open cell ratio. If the viscosity of the phenol resin is too high (for example, larger than 100000 mPa · s), the foaming rate becomes slow, and the required expansion ratio can not be obtained, which is not preferable.

The viscosity at 40 캜 refers to a value measured by the method described in (8) of " Viscosity of phenol resin at 40 캜 ". The viscosity at 40 占 폚 can be adjusted by, for example, adding a weight average molecular weight Mw of a phenol resin, a water content, a plasticizer and the like.

The viscosity rising rate constant of the phenol resin is preferably 0.05 (1 / min) to 0.5 (1 / min), more preferably 0.05 (1 / min) to 0.4 , More preferably 0.07 (1 / min) to 0.35 (1 / min) and most preferably 0.08 (1 / min) to 0.3 (1 / min). If the viscosity rising rate constant is less than 0.05 (1 / min), the curing reaction of the phenol resin does not progress sufficiently during foaming, so that the foams are dispersed to form a coarse foam, so that the compression strength is lowered. In addition, since the crosslinking reaction of the phenol resin does not sufficiently proceed, the strength of the resin portion in the foam is lowered, so that sufficient compressive strength may not be exhibited. If the viscosity elevation rate constant is larger than 0.5 (1 / min), the heat of reaction due to the curing of the phenolic resin at the initial stage of foaming becomes excessive, so that the heat is accumulated in the foam and the foaming pressure becomes too high, The compressive strength is lowered.

The viscosity rising rate constant refers to a value measured by the method described in (9) Viscosity rising rate constant of (Evaluation) to be described later. The viscosity-increasing rate constant may be, for example, a kind or a ratio of a compound having a phenyl group or an aldehyde group or a derivative thereof in synthesizing a phenol resin, a weight average molecular weight Mw of the phenol resin, The amount of catalyst added, and the like.

The tan δ (loss tangent) of the phenolic resin at 40 캜 is not particularly limited, but is preferably 0.5 or more and 40.0 or less, more preferably 0.5 or more and 35.0 or less, for example, from the standpoint of the closed cell ratio and the compressive strength , More preferably 0.5 or more and 30.0 or less.

The tan δ (loss tangent) of the phenol resin at 50 캜 is not particularly limited, but is preferably 1.25 to 65.0, more preferably 2.0 to 60.0, for example, from the standpoint of the closed cell ratio and the compressive strength Or less, more preferably 4.0 or more and 55.0 or less.

The tan δ (loss tangent) of the phenol resin at 60 캜 is not particularly limited, but is preferably from 2.0 to 90.0, more preferably from 2.0 to 80.0, for example, from the standpoint of the closed cell ratio and the compressive strength , More preferably 4.0 or more and 70.0 or less.

Among them, the phenol resin preferably has a loss tangent tan? Of from 0.5 to 40.0 at 40 占 폚, and a loss tangent tan? At 60 占 폚 of from 2.0 to 90.0, more preferably a loss tangent tan? (40 DEG C, 40.0), (60 DEG C, 40 DEG C) on the graph of the loss tangent tan? At 60 DEG C and the loss tangent tan? More preferably in a range of 40 ° C or more and 60 ° C or less, or more preferably in a range of 40 ° C or more and 60 ° C or less in a quadrangle (quadrangle formed by connecting four points by a line segment) (40 deg. C, 40.0), (60 deg. C, 2.0) and (60 deg. C, 90.0) on the graph obtained by plotting the loss tangent tan? On the abscissa and the loss tangent tan? The rectangle (the coordinates of the four points are connected by a line segment It is more preferable that it is on the side or inside of the square. That is, the loss tangent tan? At 40 占 폚, the loss tangent tan? At 50 占 폚, and the loss tangent tan? At 60 占 폚 are shown in the graph of temperature on the abscissa and loss tangent tan? More preferably in the range of 40 DEG C to 60 DEG C, and the loss tangent tan? In the range of 40 deg. C to 60 deg. C is obtained by taking the loss tangent tan? On the abscissa axis and the loss tangent tan? It is more preferable that the graph is on a straight line between y = 0.075x - 2.5 and y = 2.5x - 60 or on each straight line.

(40 ° C, 0.5), (40 ° C, 35.0), (60 ° C, 2.0) and (60 ° C, 80.0) are more preferable as the above four points on the graph obtained by taking the temperature and the loss tangent tan? , And most preferably (40 ° C, 0.5), (40 ° C, 30.0), (60 ° C, 4.0), (60 ° C, 70.0).

Even if the phenol resin has the same viscosity, the behavior at the time of heating changes due to the difference in the crosslinking state and the additive. The tan delta is the ratio of the loss elastic modulus to the storage elastic modulus, so that the larger the value is, the more easily the phenolic resin is stretched at the time of foaming, and the smaller the value, the prone to break the phenolic resin at the time of foaming. Therefore, if the loss tangent tan delta of the phenol resin is larger than the above range, the growth rate of the bubbles becomes excessively faster with respect to the foaming pressure, so that the foaming is caused and the closed cell ratio and the compressive strength are lowered. In addition, there is also a concern that since the phenol resin is not sufficiently stretched at the time of foaming, high compressive strength is not developed. If the loss tangent tan delta is less than the above range, the phenol resin tends to be broken at the time of foaming, so that the foamed film or skeleton portion of the phenol resin foam tends to be broken, so that the structure becomes discontinuous and the compression strength tends to be lowered .

In this specification, tan? (Loss tangent) is a value measured by the method described in "(10) tan?" Of (evaluation) described later. The tan delta can be determined by, for example, the kind or ratio of a compound having a phenyl group or an aldehyde group or a derivative thereof in synthesizing a phenol resin, a weight average molecular weight Mw of the phenol resin, a water content in the phenol resin, .

Examples of the compound [alpha] include those described above.

The content of the compound [alpha] in the foamable phenolic resin composition is not particularly limited, but is preferably 0.5 mass% or more and 25 mass% or more, for example, in terms of the thermal conductivity, relative to the total amount of the phenol resin and the surfactant (100 mass% More preferably 2 mass% or more and 20 mass% or less, further preferably 3 mass% or more and 18 mass% or less, particularly preferably 3 mass% or more and 15 mass% or less.

In the present embodiment, the total content of the compound a and / or the hydrocarbon is not particularly limited, but may be, for example, 3.0% by mass or more and 25.0% by mass or more (relative to the total amount of the phenol resin and the surfactant By mass or less, more preferably 3.0% by mass or more and 22.5% by mass or less, still more preferably 5.0% by mass or more and 20.0% by mass or less, particularly preferably 6.0% by mass or more and 18.0% , And most preferably not less than 6.0 mass% and not more than 15.0 mass%. If the addition amount is less than 3.0 mass%, it becomes very difficult to obtain the required expansion ratio and the foam becomes excessively high in density, and a good foam can not be obtained, which is not preferable. If the addition amount is more than 25.0 mass%, the viscosity of the phenol resin is lowered due to the plasticizing effect of the compound alpha, and excess foaming is caused by excessively large amount of addition, so that the foaming of the foam is blown, The physical properties such as heat insulation performance and compressive strength are lowered, which is not preferable.

In the present embodiment, an inorganic gas such as nitrogen or argon is added to the total amount of the above-mentioned compounds? And / or hydrocarbons together with the compound? As a bubbling agent in order to improve the decrease of the independent bubble ratio and the compression strength due to the phenol resin plasticization. , More preferably not less than 0.05% and not more than 3.0%, more preferably not less than 0.1% and not more than 2.5%, particularly preferably not less than 0.1% and not more than 1.5% , Most preferably not less than 0.3% and not more than 1.0%. If the addition amount is less than 0.05%, the effect as a foam nucleating agent becomes insufficient. If the addition amount exceeds 5.0%, the foaming pressure of the phenolic resin foam becomes too high during the foaming and curing process, It is not preferable because it becomes a coarse foam having a low compressive strength.

Examples of the nitrogen-containing compound include those described above.

The nitrogen-containing compound may be added directly to the phenol resin during the reaction or at the timing near the end of the reaction, or may be mixed with the phenol resin reacted with formaldehyde in advance.

The content of the nitrogen-containing compound is not particularly limited. However, from the viewpoints of reduction of a compound or an aldehyde group-containing compound diffusing from the phenol resin foam and flexibility of the phenol resin foam, the total amount of the phenol resin More preferably 2% by mass or more and 10% by mass or less, particularly preferably 3% by mass or more and 8% by mass or less,

Examples of the plasticizer include phthalic acid esters, glycol ethers such as ethylene glycol and diethylene glycol, and among them phthalic acid esters are preferably used. In addition, an aliphatic hydrocarbon or an alicyclic hydrocarbon, or a mixture thereof, may be used. These plasticizers may be used alone or in combination of two or more.

Examples of the flame retardant include phosphorus compounds such as bromine compounds such as tetrabromobisphenol A and decabromodiphenyl ether commonly used as flame retardants, aromatic phosphoric acid esters, aromatic condensed phosphoric acid esters, halogenated phosphoric acid esters, Compounds, ammonium polyphosphate, antimony trioxide, and antimony pentoxide. These flame retardants may be used alone or in combination of two or more.

As the surfactant, those generally used in the production of a phenolic resin foam may be used. Among them, a nonionic surfactant is effective. For example, an alkylene oxide which is a copolymer of ethylene oxide and propylene oxide, Condensates of alkylene oxide and castor oil, condensates of alkylene oxide and nonylphenol, alkylphenol such as dodecylphenol, polyoxyethylene alkyl ether having 14 to 22 carbon atoms in the alkyl ether moiety, and polyoxyethylene fatty acid ester , Silicone compounds such as polydimethylsiloxane, and polyalcohols are preferable. These surfactants may be used alone or in combination of two or more.

The amount of the surfactant to be used is not particularly limited, but is preferably in the range of 0.3 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the phenol resin.

The curing catalyst may be an acidic curing catalyst capable of curing the phenolic resin, for example, an anhydride curing catalyst is preferred. As the anhydride curing catalyst, phosphoric anhydride or anhydridesulfonic acid is preferable. Examples of the anhydride arylsulfonic acid include toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, substituted phenolsulfonic acid, zylenol sulfonic acid, substituted xylenol sulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid and naphthalenesulfonic acid. They may be used in combination of two or more. The curing catalyst may be diluted with a solvent such as ethylene glycol or diethylene glycol.

The amount of the curing catalyst to be used is not particularly limited, but is preferably 3 parts by mass or more and 30 parts by mass or less based on 100 parts by mass of the phenol resin. The amount may be 3 parts by mass or more and 30 parts by mass or less based on the total amount (100 parts by mass) of the phenol resin and the surfactant.

Examples of the curing aid include resorcinol, cresol, saligenin (o-methylol phenol), p-methylol phenol and the like. The curing auxiliary may be used singly or in combination of two or more kinds.

The foamable phenol resin composition is not particularly limited, but may be obtained by mixing the phenol resin, the surfactant, the compound a, the hydrocarbon, the curing catalyst, the nitrogen-containing compound, the plasticizer or other materials, Can be obtained.

The phenol resin foam can be produced by, for example, continuously discharging the above-described foamable phenolic resin composition on a running face material, and coating the surface of the foamable phenolic resin composition on the opposite side to the face contacting the face material with another face material And a continuous production method comprising foaming and heat curing the foamable phenolic resin composition. In another embodiment, the above-mentioned foamable phenolic resin composition may be obtained by a batch production method of pouring the foamed phenolic resin composition into a mold inside which is coated with a face plate, or a mold coated with a mold release agent, have. The phenol resin foam obtained by the batch production method may be sliced in the thickness direction as required.

Further, in the present specification, a laminate (a laminate including a face plate and a phenol resin foam) in which a phenol resin foam is laminated on a face material is sometimes referred to as a phenol resin foam laminate. The phenolic resin foam laminate may have one face sheet or two face sheets (upper face material and lower face material) formed on the first face (upper face) and the second face (lower face) of the phenolic resin foam . The face material is preferably formed in contact with the phenol resin foam.

The face material is not particularly limited, but it is preferable to remove moisture (moisture contained in the phenol resin, moisture generated during the curing reaction (dehydration condensation reaction), etc.) generated during foaming and curing of the foamable phenolic resin composition, For example, a face plate having gas permeability is preferable from the viewpoints of preventing breakage due to an excessively high internal pressure and further improving the closed cell ratio. Examples of the face plate having gas permeability include synthetic fiber nonwoven fabrics such as nonwoven fabrics made of polyester (nonwoven fabric made of polyethylene terephthalate) and nonwoven fabrics made of polyamide (nylon nonwoven fabric, etc.), glass fiber nonwoven fabrics, Paper, a metal film having a through hole (a metal foil having a through hole and paper, a laminate reinforced with glass cloth or glass fiber), and the like. Among them, a PET fiber nonwoven fabric, a glass fiber nonwoven fabric, and aluminum having a through hole are preferable from the viewpoints of flame retardance, surface material adhesion strength, and prevention of leakage of the foamable phenolic resin composition. Further, the metal film having the through-hole can be produced by a process such as punching a hole penetrating in the thickness direction. In the phenol resin foam laminate, moisture is easily dissipated from the phenol resin foam during the curing by blowing with a gas permeable face material, so that the foaming of the foam by the steam can be suppressed. From this point of view, it is preferable that the phenolic resin foam has a face material on the first face (upper face) and the second face (lower face), and both face materials are gas permeable.

The gas permeability of the face material means a face material having a transmittance of oxygen measured according to ASTM D3985-95 of 4.5 cm 3/24 h ㎡ m 2 or more.

The face plate preferably has flexibility, for example, for the purpose of preventing the face plate from being broken at the time of production. Examples of the face material having flexibility include synthetic fiber nonwoven fabric, synthetic fiber woven fabric, glass fiber nonwoven fabric, glass fiber woven fabric, glass fiber nonwoven fabric, glass fiber bicomponent paper, papers, Or a combination thereof, and the like. The face plate may contain a flame retardant to impart flame retardancy. Examples of the flame retardant include bromine compounds such as tetrabromobisphenol A and decabromodiphenyl ether; phosphorus or phosphorus compounds such as aromatic phosphoric acid esters, aromatic condensed phosphoric acid esters, halogenated phosphoric acid esters, and red phosphorus; ammonium polyphosphate; antimony trioxide; Antimony compounds such as antimony, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and carbonates such as calcium carbonate and sodium carbonate. The flame retardant may be kneaded in fibers of the face material or may be added to a binder of a face material such as acrylic, polyvinyl alcohol, vinyl acetate, epoxy, and unsaturated polyester. The face material may be surface-treated with a water-repellent agent such as a fluororesin system, a silicone resin system, a wax emulsion system, a paraffin system, an acrylic resin paraffin wax combination system, or an asphalt-based waterproofing agent. These water repellent agents and waterproofing agents may be used alone or may be added to the face plate by adding the flame retardant.

The temperature of the foamable phenolic resin composition at the time of discharging the foamable phenolic resin composition on the face material is, for example, preferably 25 占 폚 or more and 50 占 폚 or less, more preferably 30 占 폚 or more and 45 占 폚 or less. When the temperature is 50 DEG C or lower, foaming takes place moderately, and a smooth foaming sheet is obtained. When the temperature is 25 占 폚 or higher, curing takes place moderately, resulting in balanced foaming and curing.

A foamed phenolic resin composition sandwiched between two face plates can foam between two face plates. In order to cure the foamed phenol resin composition (foam), for example, the following first and second ovens can be used.

As the first oven, for example, an endless steel belt type double conveyor or a slat type double conveyor is used, and foaming and curing are performed in an atmosphere of 60 ° C or more and 110 ° C or less. In this oven, the uncured foam is cured while being formed into a plate, whereby a partially cured foam can be obtained. The temperature in the first oven may be uniform throughout the whole range, or may be a plurality of temperature zones.

The second oven preferably generates hot air at 70 ° C or more and 120 ° C or less to post-cure the partially cured foam in the first oven. The partially cured foam boards may be superimposed at regular intervals using spacers or trays. If the temperature in the second oven is excessively high, the pressure inside the bubbles of the foam becomes excessively high, causing the foaming. If the temperature is too low, it may take too much time for the reaction of the phenol resin to proceed. Or less.

In the first and second ovens, the internal temperature of the phenolic resin foam is preferably 60 ° C to 105 ° C, more preferably 70 ° C to 100 ° C, further preferably 75 ° C to 95 ° C, And most preferably 75 deg. C or more and 90 deg. C or less. The internal temperature of the phenolic resin foam can be measured, for example, by introducing a thermocouple and data recording function into the foamable phenolic resin composition in the oven.

When the compound [alpha] is used, the phenol resin is plasticized due to high compatibility with the phenol resin of the compound [alpha], so that viscosity increase due to the curing reaction of the phenol resin in the step of foam hardening may be lost. As a result, in the same oven heating as in the prior art, it is feared that the phenol resin foam can not obtain sufficient hardness. Therefore, it is preferable that the sum of the residence times in the first and second ovens is longer than that in the case of using a conventional hydrocarbon. The total residence time in the first and second ovens is preferably, for example, from 3 minutes to 60 minutes, more preferably from 5 minutes to 45 minutes, particularly preferably from 5 minutes to 30 minutes, Preferably not less than 7 minutes and not more than 20 minutes. If the residence time in the oven is too short, the phenolic resin foam will leave the oven in an uncured state, resulting in a poor phenolic foam foam having poor dimensional stability. If the residence time in the oven is too long, the drying of the phenolic resin foam becomes excessively low, and the water content becomes too low, which is not preferable because the board sucks a large amount of moisture in the air after leaving the oven.

The foaming and curing method of the foamable phenolic resin composition for obtaining the phenolic resin foam of the present embodiment is not limited to the above-described method.

The phenolic resin foam of the present invention can be used, for example, as a heat insulating material for housing construction, industrial or industrial use.

As described above, according to the production method according to the present embodiment, it is possible to provide a phenolic resin foam which is low in environmental load, high in compressive strength, and excellent in handling and fixing cost at the time of construction.

Example

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

(evaluation)

The following items were measured and evaluated for phenol resin and phenol resin foam in Examples and Comparative Examples.

(1) Identification of the kind of the compound α and / or the hydrocarbon in the phenol resin foam

First, the standard gas of chlorinated hydrofluoroolefin, non-chlorinated hydrofluoroolefin, and halogenated hydrocarbon was used to determine the holding time under the following GC / MS measurement conditions.

The face material was peeled off from the phenol resin foamed laminate obtained in the examples and the comparative example, and about 10 g of the phenol resin foam sample and a metal strip were sealed in a 10-liter container (product name: "Tedlar bag") and injected with 5 L of nitrogen. The sample was cut using a line from the top of the Tedlar bag and crushed finely. Subsequently, the sample was placed in a Tedlar bag and incubated for 10 minutes in an incubator warmed to 81 ° C. 100 [mu] l of gas generated in a Tedlar bag was sampled and subjected to GC / MS analysis under the following measurement conditions to identify the kind of the compound [alpha] and / or the hydrocarbon in the phenol resin foam.

The presence or absence of chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins and halogenated hydrocarbons was confirmed by GC / MS analysis. The kinds of the chlorinated hydrofluoroolefin, the non-chlorinated hydrofluoroolefin and the halogenated hydrocarbon were identified from the previously obtained holding time and mass spectrum. With respect to the hydrocarbons, kinds were determined by the holding time and the mass spectrum. Separately, the detection sensitivity of the generated gas components was measured by standard gas, and the composition ratio was calculated from the detection area area and detection sensitivity of each gas component obtained by GC / MS. The mass ratio of each gas component was calculated from the composition ratio and the molar mass of each gas component identified.

(GC / MS measurement conditions)

Gas chromatography: "Agilent 7890 type" manufactured by Agilent Technologies

Column: " InertCap 5 " (inner diameter: 0.25 mm, film thickness: 5 m, length: 30 m)

Carrier gas: helium

Flow rate: 1.1 ml / min

Temperature of inlet: 150 ° C

Injection method: Split method (1:50)

Sample injection volume: 100 μl

 Column temperature: maintained at -60 캜 for 5 minutes, raised to 150 캜 at 50 캜 / min, maintained for 2.8 min

Mass analysis: "Q1000GC type" manufactured by Nippon Electric Co.,

Ionization method: Electron ionization method (70 eV)

Scanning range: m / Z = 10 to 500

Voltage: -1300 V

Ion source temperature: 230 ° C

Interface temperature: 150 ℃

(2) Foam density

A board having a size of 20 cm was cut out from the phenol resin foam laminate obtained in Examples and Comparative Examples, and the face material was removed to measure the mass and apparent volume of the phenol resin foam. The density (apparent density) was calculated according to JIS K 7222 using the obtained mass and apparent volume.

(3) Independent air bubble rate

With reference to ASTM D 2856-94 (1998) A, it was measured by the following method.

Cubic specimens having a length of about 25 mm and a length of about 25 mm were cut out from the central portion in the thickness direction of the phenol resin foam in the phenol resin foamed laminate obtained in Examples and Comparative Examples. When a thin specimen with a uniform thickness of 25 mm was not obtained, a specimen having a uniform thickness was prepared by slicing the cut surface of a cubic specimen of about 25 mm in length by about 1 mm. The length of each side was measured by Nogus, and the apparent volume (V 1: cm 3) was measured and the mass of the specimen (W: four digits of the significant digits, g) was measured. Subsequently, the closed space volume (V2: cm3) of the specimen was measured according to the method described in Method A of ASTM D 2856 using an air peak furnace (Tokyo Science Co., product name "MODEL1000").

The average cell diameter (t: cm) was measured according to (3) the average cell diameter measuring method described above, and the surface area (A: cm 2) of the test piece was measured from the length of each side of the test piece.

(VA: cm < 3 >) of the cut bubbles on the surface of the test piece was calculated from the equation VA = (A x t) /1.14. The volume (VS: cm 3) of the solid portion constituting the bubble wall contained in the test piece was calculated by the formula VS = specimen mass (W) / 1.3, with the density of the solid phenolic resin being 1.3 g / cm 3.

The closed cell ratio was calculated by the following formula (1).

(%) = [(V 2 - VS) / (V 1 - VA - VS)] × 100 (One)

Six measurements were made on the foam sample under the same manufacturing conditions, and the average value was taken as a representative value.

(4) 10% compressive strength

Test pieces having a length of 100 mm and a width of 100 mm were cut out from the phenol resin foamed laminate obtained in Examples and Comparative Examples, and the face materials were removed to obtain test pieces. The obtained test pieces were cured in an atmosphere of a temperature of 23 ° C and a relative humidity of 50% until the difference in the two weighing values performed at intervals of 24 hours became 0.1% or less. The cured test piece was subjected to 10% compressive strength according to JIS K 7220.

(5) Absolute value of dimensional change after three cycles of dry and wet repetition

A test piece having a length of 300 mm and a width of 300 mm was cut out from the phenol resin foamed laminate obtained in Examples and Comparative Examples, and the face material was removed to obtain a test piece. The obtained test piece was allowed to stand for 2 weeks in an atmosphere at a temperature of 23 캜 and a relative humidity of 50%. Thereafter, the dimensions of the test piece in the lateral (W) and longitudinal (L) directions were measured to obtain dimensions A _0W and A _0L at the start of the test. After 12 hours from the start of the test, the test piece was left under an atmosphere of a temperature of 50 ° C and a relative humidity of 95%. From 12 hours to 24 hours after the start of the test, the test piece was left under an atmosphere of a temperature of 50 ° C and a relative humidity of 35%. One cycle from the start of the test to 24 hours after the start of the test was performed, and the test piece was left until the end of the three cycles. The 3 cycle end is 72 hours after the start of the test. After three cycles, that is, 72 hours after the start of the test, the dimensions of the test piece in the transverse (W) and longitudinal (L) directions were measured to obtain A _72W and A _72L . The absolute value of the dimensional change amount after 3 cycles of dry and wet repetition was calculated by the following equations (2) and (3). The absolute value of the dimensional change amount after three cycles of dry and wet repetition refers to the absolute value of the dimensional change amount in the vertical and horizontal directions, whichever is larger. The width and transverse direction of the specimen refers to the direction orthogonal to the thickness direction of the product.

Absolute value of dimensional change amount in the width direction after three cycles of dry / wet repetition = A _72W - A _0W (2)

Absolute value of dimensional change amount in the longitudinal direction after three cycles of dry / wet repetition = A _72L - A _0L

 (3)

(6) brittle

The brittleness was calculated in accordance with JIS A 9511 (2003) 5.1.4 as follows. Twelve test pieces were cut out from the phenol resin foamed laminate obtained in the Examples and Comparative Examples, each of which had been cut into a cubic shape of 25 ± 1.5 mm so as to include a face with a face-skinned surface on one face, . The test apparatus is equipped with a shaft on the outside of the central portion of the 197 mm surface of an oak wood box having an inner diameter of 191 x 197 x 197 mm and attaching a door to one side of the box and sealing the dust out of the box. And it is possible to rotate at 60 ± 2 rotations per minute. Twenty - four dice - shaped dice with a dry specific gravity of 0.65 and dimensions of 19 ± 0.8 ㎜ were placed in the measuring device together with the test pieces and sealed, and then the wooden box was rotated by 600 ± 3 degrees. After completion of the rotation, the contents of the box were carefully transferred to a net having an object nominal size of 9.5 mm in accordance with JIS Z 8801, sieved to remove small pieces, and the remaining test pieces were taken from the net and the mass was measured. The brittleness was obtained by the following equation.

(%) = 100 x (m ₀ - m ₁ ) / m ₀

(M ₀ : mass (g) of the test piece before the test, m ₁ : mass (g) of the test piece after the test)

(7) Weight average molecular weight Mw of phenolic resin

Measurement was carried out under the following conditions by gel permeation chromatography (GPC) measurement. From the calibration curve obtained by the following standard substances (standard polystyrene, 2-hydroxybenzyl alcohol and phenol) And the weight average molecular weight Mw of the phenol resin was determined.

Pretreatment :

About 10 mg of the phenol resin was dissolved in 1 ml of N, N dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., high-speed liquid chromatograph), and the solution was filtered through a 0.2 탆 membrane filter, and used as a measurement solution.

Measuring conditions :

Measurement apparatus: Shodex System 21 (manufactured by Showa Denko KK)

Column: Shodex asahipak GF-310HQ (7.5 mm ID × 30 cm)

Eluent: 0.1% by mass of lithium bromide was dissolved in N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high-speed liquid chromatograph) and used.

Flow rate: 0.6 ml / min

Detector: RI detector

Column temperature: 40 DEG C

Standard material: standard polystyrene (Shodex standard SL-105 manufactured by Showa Denko KK), 2-hydroxybenzyl alcohol (manufactured by Sigma Aldrich), phenol (manufactured by Kanto Kagaku Co., Ltd., limited edition)

(8) Viscosity of phenol resin at 40 占 폚

0.5 ml of a phenol resin was weighed out and set on a rotational viscometer (manufactured by TOKI INDUSTRIAL CO., LTD., Type R-100, rotor part 3 DEG x R-14). The number of revolutions of the rotor was set so that the viscosity of the phenolic resin to be measured was in the range of 50 to 80% with respect to the upper limit viscosity measured by the apparatus. The measurement temperature was set at 40 占 폚, and the value of the viscosity after 3 minutes from the start of the measurement was used as the measurement value.

(9) Viscosity rising rate constant

A curing catalyst of 70% by mass of xylene sulfonic acid and 30% by mass of diethylene glycol was precisely weighed to a phenol resin in an amount of 10% by mass to the phenol resin used in the examples and comparative examples having a mass of 10 g, Mix well.

0.5 ml of the mixture of the phenol resin and the curing catalyst is set in a rotational viscometer (R-100 type, manufactured by TOKI INDUSTRIAL CO., LTD., Rotor part is 3 DEG x R-14) and the viscosity at 40 DEG C is measured at intervals of 30 seconds. The X axis of the measurement result is plotted as a time (minutes) from the start of viscosity measurement, and the Y axis is plotted as a logarithm of the viscosity (mPa · s). The time is assumed to be a straight line between 4 minutes and 10 minutes, and this "slope (1 / (minute))" is obtained.

This " slope " was defined as " viscosity rising rate constant ".

(10) tan?

A parallel plate type jig made of aluminum having a diameter of 50 mm was attached to a viscoelasticity measuring apparatus (trade name "ARES", manufactured by TA Instruments). Of the two parallel plates installed up and down, about 2 ml of phenol resin was provided on the lower parallel plate. Thereafter, the gap of the parallel plate was set to 0.5 mm, and the resin evacuated from the periphery of the parallel plate was scraped with a spatterer. Subsequently, an oven was provided to surround the parallel plate. The temperature was set at 40 占 폚, 50 占 폚 and 60 占 폚, and tan? Was measured at each temperature under the following measurement conditions. The measurement was performed after the set temperature was reached, and the value after 5 minutes was set as the value of the read tan?.

The measurement was carried out by measuring the gap of the upper and lower parallel plates at 0.5 mm, the deformation amount at 10%, and the frequency at 50 Hz. The temperature of the oven was adjusted so that the temperature of the thermocouples provided on the rear side of the lower parallel plate among the thermocouples provided on the back surface of the parallel plate in the oven and on the lower side became a predetermined temperature.

The obtained tan δ at 40 ° C., tan δ at 50 ° C., and δ at 60 ° C. were plotted on a graph having the abscissa as the temperature and the ordinate as the tan δ.

<Synthesis of phenol resin A>

3500 kg of a 52% by mass aqueous formaldehyde solution and 2743 kg of 99% by mass phenol were fed into the reactor, stirred by a propeller rotary stirrer, and the temperature of the reactor internal temperature was adjusted to 40 占 폚 by a hot oven. Then, a 50 mass% aqueous sodium hydroxide solution was added until the pH of the reaction solution became 8.7. The reaction solution was heated to 85 ° C over 1.5 hours, and then, at the stage where the Ostwald viscosity reached 73 centistokes (= 73 × 10 ^-6 m 2 / s, measured value at 25 ° C) Was cooled, and 400 kg of urea was added. Thereafter, the reaction solution was cooled to 30 DEG C, and a 50 mass% aqueous solution of paratoluenesulfonic acid monohydrate was added until the pH reached 6.4. The obtained reaction solution was concentrated by a thin film evaporator until the water content in the phenol resin reached 7.4 mass%, and as a result, the viscosity at 40 캜 was 22,000 mPa..

The viscosity at 40 캜 was changed by adjusting the injection amount of a 52% by mass formaldehyde aqueous solution shown in Table 1, the injection amount of 99% by mass of phenol, the amount of oustatic solution, the amount of urea added, and the water content in the phenol resin using a thin film evaporator Phenol resin B to L were obtained in the same manner as phenol resin A.

(Example 1)

2.0 parts by mass of a mixture containing 50% by mass and 50% by mass of a block copolymer of ethylene oxide-propylene oxide and polyoxyethylene dodecylphenyl ether as a surfactant per 100 parts by mass of the phenol resin A Lt; / RTI &gt; 11 parts by mass of the compound A shown in Table 2 and 14 parts by mass of a mixture of 80% by mass of xylene sulfonic acid and 20% by mass of diethylene glycol as a curing catalyst were added to 100 parts by mass of the phenol resin mixed with the surfactant, Lt; RTI ID = 0.0 &gt; C, &lt; / RTI &gt; to obtain a foamable phenolic resin composition.

The resulting foamable phenolic resin composition was supplied on a moving face material (a bottom material). The foamable phenolic resin composition supplied on the face material was formed so that the face opposite to the face contacting with the face material was covered with another face material (upper face material) and sandwiched between the two face materials, Type double conveyor in a first oven. The foamable phenolic resin composition was cured for a retention time of 15 minutes and then cured in an oven at 110 DEG C for 2 hours to obtain a phenol resin foamed article and a phenol resin foamed article laminated with a phenol resin foamed article on a faceplate.

A glass fiber nonwoven fabric (trade name &quot; Dura Glass Type DH70 (basis weight 70 g / m &lt; 2 &gt;) &quot;, manufactured by Jones Mannville) was used as the upper surface material and the lower surface material.

(Example 2)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that Compound B was used instead of Compound A and 9 parts by mass of Compound B was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 3)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that Compound C was used instead of Compound A and 8.5 parts by mass of Compound C was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 4)

A compound D was used instead of the compound A, 14 parts by mass of a compound D was added to 100 parts by mass of a phenol resin mixed with a surfactant, and a polyester nonwoven fabric (trade name: Spanbond E05030 basis weight 30 g / m &lt; 2 &gt; &quot; manufactured by Asahi Chemical Industry Co., Ltd.) was used in place of the phenol resin foamed product.

(Example 5)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that Compound E was used instead of Compound A and 6 parts by mass of Compound E was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 6)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that Compound F was used instead of Compound A and 8 parts by mass of Compound F was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 7)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that Compound G was used instead of Compound A and 11 parts by mass of Compound G was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 8)

A phenol resin B as a phenol resin, 11 parts by mass of a compound A to 100 parts by mass of a phenol resin mixed with a surfactant, and a polyester nonwoven fabric (trade name: Spanbond E05030 basis weight 30 g / m &lt; 2 &gt; &quot; manufactured by Asahi Chemical Industry Co., Ltd.) was used in place of the phenol resin foamed product.

(Example 9)

A phenol resin C as a phenol resin, 11 parts by mass of a compound A to 100 parts by mass of a phenol resin mixed with a surfactant, and a polyester nonwoven fabric (trade name: Spanbond E05030 basis weight 30 g / m &lt; 2 &gt;, manufactured by Asahi Chemical Industry Co., Ltd.) was used in place of the phenol resin foamed product.

(Example 10)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that phenol resin D was used as the phenol resin and 12 parts by mass of the compound A was added to 100 parts by mass of the phenol resin mixed with the surfactant.

(Example 11)

A phenol resin foam was obtained in the same manner as in Example 1 except that the phenol resin D as the phenol resin and the compound F were used in place of the compound A and 6 parts by mass of the compound F was added to 100 parts by mass of the phenol resin mixed with the surfactant, Phenol resin foam laminate.

(Example 12)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that phenol resin E was used as the phenol resin and 12 parts by mass of the compound A was added to 100 parts by mass of the phenol resin mixed with the surfactant.

(Example 13)

A phenol resin foam was prepared in the same manner as in Example 1 except that phenol resin E as the phenol resin, compound D instead of the compound A, and 15 parts by mass of the compound D were added to 100 parts by mass of the phenol resin mixed with the surfactant, Phenol resin foam laminate.

(Example 14)

A phenol resin foam was prepared in the same manner as in Example 1 except that the phenol resin E as the phenol resin and the compound F were used instead of the compound A and 7 parts by mass of the compound F was added to 100 parts by mass of the phenol resin mixed with the surfactant, Phenol resin foam laminate.

(Example 15)

A phenol resin foam was prepared in the same manner as in Example 1, except that phenol resin E was used as the phenol resin, compound G was used instead of the compound A, and 12 parts by mass of the compound G was added to 100 parts by mass of the phenol resin mixed with the surfactant. Phenol resin foam laminate.

(Example 16)

A phenol resin F as a phenol resin, a compound B in place of the compound A, and 9 parts by mass of a compound B to 100 parts by mass of a phenol resin mixed with a surfactant, as a top surface material and a bottom surface material, (Product name: "Spanbond E05030 30 g / m 2", manufactured by Asahi Kasei Fibers Co., Ltd.) was used in place of phenol resin foamed product and phenol resin foamed laminate.

(Example 17)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that the phenol resin G was used as the phenol resin and 13 parts by mass of the compound A was added to 100 parts by mass of the phenol resin mixed with the surfactant.

(Example 18)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that Compound H was used instead of Compound A and 7 parts by mass of Compound H was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 19)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that Compound I was used instead of Compound A and 11 parts by mass of Compound I was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 20)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1, except that Compound J was used instead of Compound A and 11 parts by mass of Compound J was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 21)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that Compound K was used instead of Compound A and 11 parts by mass of Compound K was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 22)

A phenol resin foam was prepared in the same manner as in Example 1 except that the phenol resin E as the phenol resin and the compound L instead of the compound A were used and 9 parts by mass of the compound L was added to 100 parts by mass of the phenol resin mixed with the surfactant, Phenol resin foam laminate.

(Example 23)

A phenol resin foam was prepared in the same manner as in Example 1 except that the phenol resin E as the phenol resin and the compound M instead of the compound A were used and 9 parts by mass of the compound M was added to 100 parts by mass of the phenol resin mixed with the surfactant, Phenol resin foam laminate.

(Example 24)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that Compound N was used instead of Compound A and 10 parts by mass of Compound N was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 25)

A foamable phenol resin composition was obtained in the same manner as in Example 1 except that phenol resin E was used as the phenol resin and 10 parts by mass of the compound A was added to 100 parts by mass of the phenol resin mixed with the surfactant. The foamable phenolic resin composition was poured into a mold made of aluminum having an inner diameter of 1000 mm, a width of 1000 mm and a thickness of 1000 mm covered with a face plate and closed. The periphery of the mold and the upper and lower surfaces were fixed by a clamp so as not to be opened by the foaming pressure. Introduced into an oven heated to 85 캜, and cured for 60 minutes. Thereafter, the phenol resin foam was taken out from the mold and heated in an oven at 110 DEG C for 5 hours to obtain a block-like phenol resin foam. The face plate used was the same as in Example 1. The obtained block-shaped phenol resin foam was sliced at a thickness of 50 mm from the center in the thickness direction to obtain a plate-like phenol resin foam.

(Example 26)

A phenol resin foam, a phenol resin foam, and a phenol resin foam were prepared in the same manner as in Example 1, except that an aluminum sheet reinforced with glass fiber having gas permeability, which had been pre-punched through a through hole having a diameter of 0.5 mm at intervals of 20 mm, To obtain a foam laminate.

(Example 27)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1, except that 2 parts by mass of hexamethyldisiloxane was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 28)

A phenol resin foam and a phenol resin foam laminate were prepared in the same manner as in Example 1 except that Compound G was used instead of Compound A and 2 parts by mass of hexamethyldisiloxane was added to 100 parts by mass of a phenol resin mixed with a surfactant .

(Example 29)

A phenol resin foam and a phenol resin foam laminate were produced in the same manner as in Example 1 except that Compound I was used instead of Compound A and 2 parts by mass of hexamethyldisiloxane was added to 100 parts by mass of a phenol resin mixed with a surfactant .

(Example 30)

Compound O was used instead of Compound A, and 7 parts by mass of Compound O was added to 100 parts by mass of a phenol resin mixed with a surfactant. To 100 parts by mass of a phenol resin mixed with a surfactant, 1 mass of phthalic acid ester as a plasticizer A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1. [

(Example 31)

Compound P was used instead of Compound A, and 7 parts by mass of Compound P was added to 100 parts by mass of a phenol resin mixed with a surfactant. To 100 parts by mass of a phenol resin mixed with a surfactant, 1 part by mass of phthalic acid ester as a plasticizer A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1. [

(Example 32)

Phenol resin D was used as the phenol resin, compound O was used instead of the compound A, 7 parts by mass of the compound O was added to 100 parts by mass of the phenol resin mixed with the surfactant, 100 parts by mass of the phenol resin mixed with the surfactant And 1 part by mass of a phthalic acid ester as a plasticizer was added to the mixture obtained in Example 1, to obtain a phenol resin foam and a phenol resin foam laminate.

(Example 33)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that Compound Q was used instead of Compound A and 7 parts by mass of Compound Q was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 34)

9 parts by mass of the compound R was added to 100 parts by mass of a phenol resin in which a phenol resin E was used instead of the compound A and a compound R was mixed with a surfactant and 100 parts by mass of a phenol resin And 1 part by mass of a phthalic acid ester as a plasticizer was added to the mixture obtained in Example 1, to obtain a phenol resin foam and a phenol resin foam laminate.

(Example 35)

Except that the phenol resin F was used as the phenol resin, the compound S was used instead of the compound A, and 10 parts by mass of the compound S was added to 100 parts by mass of the phenol resin mixed with the surfactant, To obtain a resin foam and a phenol resin foam laminate.

(Example 36)

Compound T was used instead of Compound A, and 6 parts by mass of Compound T was added to 100 parts by mass of a phenol resin mixed with a surfactant. To 100 parts by mass of a phenol resin mixed with a surfactant, 1 part by mass of phthalic acid ester as a plasticizer A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1. [

(Example 37)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that Compound U was used instead of Compound A and 7 parts by mass of Compound U was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Example 38)

Compound V was used instead of Compound A, and 6 parts by mass of Compound V was added to 100 parts by mass of a phenol resin mixed with a surfactant. To 100 parts by mass of a phenol resin mixed with a surfactant, 1 mass of phthalic acid ester as a plasticizer A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1. [

(Example 39)

Except that the phenol resin B was used as the phenol resin, the compound W was used instead of the compound A, and 10 parts by mass of the compound W was added to 100 parts by mass of the phenol resin mixed with the surfactant, To obtain a resin foam and a phenol resin foam laminate.

(Example 40)

Compound X was used instead of Compound A, and 11 parts by mass of Compound X was added to 100 parts by mass of a phenol resin mixed with a surfactant. To 100 parts by mass of a phenol resin mixed with a surfactant, 1 mass of phthalic acid ester as a plasticizer A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1. [

(Example 41)

A phenol resin F was used as the phenol resin, Compound Y was used instead of the compound A, 7 parts by mass of the compound Y was added to 100 parts by mass of the phenol resin mixed with the surfactant, 100 parts by mass of the phenol resin And 1 part by mass of a phthalic acid ester as a plasticizer was added to the mixture obtained in Example 1, to obtain a phenol resin foam and a phenol resin foam laminate.

(Example 42)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that Compound Z was used instead of Compound A and 10 parts by mass of Compound Z was added to 100 parts by mass of a phenol resin mixed with a surfactant.

(Comparative Example 1)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that phenol resin H was used as the phenol resin and 11 parts by mass of the compound A was added to 100 parts by mass of the phenol resin mixed with the surfactant.

(Comparative Example 2)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that phenol resin I was used as the phenol resin and 11 parts by mass of the compound A was added to 100 parts by mass of the phenol resin mixed with the surfactant.

(Comparative Example 3)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that the phenol resin J was used as the phenol resin and 11 parts by mass of the compound A was added to 100 parts by mass of the phenol resin mixed with the surfactant.

(Comparative Example 4)

A phenol resin foam and a phenol resin foam laminate were obtained in the same manner as in Example 1 except that the phenol resin K was used as the phenol resin and 10 parts by mass of the compound A was added to 100 parts by mass of the phenol resin mixed with the surfactant.

(Comparative Example 5)

A phenol resin foam was obtained in the same manner as in Example 1 except that phenol resin L was used as the phenol resin, compound B was used instead of the compound A, and 9 parts by mass of the compound B was added to 100 parts by mass of the phenol resin mixed with the surfactant. Phenol resin foam laminate.

Tables 3, 4 and 5 show the resins used in the phenolic resin foams obtained in the Examples and Comparative Examples, their properties, the compounds, and the properties and evaluation results of the obtained phenolic resin foams.

The phenolic resin foams of Examples 1 to 32 were excellent in the strength against compression, the weight of the heat insulating material was not excessively heavy, handling was excellent, and efficiency at the time of construction was improved. In addition, there were few members and spheres used for fixing the phenol resin foam, and it was also excellent in cost at the time of construction.

The phenolic resin foams of Examples 1 to 32 were found to have cracks or cracks on the surface when the phenolic resin foamed article walked on the floor or on a flat roof in construction or during maintenance No problems have occurred.

On the other hand, the phenolic resin foams of Comparative Examples 1 to 5 had insufficient compressive strength due to low compressive strength with respect to density. Particularly, the phenolic resin foams of Comparative Examples 1 and 3 to 5 had a low closed cell ratio and a poor thermal conductivity.

Industrial availability

The phenolic resin foam of the present embodiment can be suitably used for a heat insulating material for housing use because it has a low load on the environment, high compressive strength, and excellent handling and fixing cost at the time of construction.

Claims (13)

Chlorinated hydrofluoroolefin, chlorinated hydrofluoroolefin, chlorinated hydrofluoroolefin, non-chlorinated hydrofluoroolefin, and halogenated hydrocarbon,
A density of 20 kg / m 3 or more and 100 kg / m 3 or less,
The closed cell ratio is 80% or more and 99% or less,
10% compression strength and the density satisfy the relation of the following formula.
C ≥ 0.5X - 7
(Wherein C represents 10% compressive strength (N / cm2) and X represents density (kg / m3) The method according to claim 1,
At least one member selected from the group consisting of the chlorinated hydrofluoroolefin and the non-chlorinated hydrofluoroolefin, and the halogenated hydrocarbon. 3. The method according to claim 1 or 2,
At least one species selected from the group consisting of the chlorinated hydrofluoroolefin and the non-chlorinated hydrofluoroolefin is 1-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3- Trifluoropropene, 1,3,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene and 1,1,1,4,4, Hexafluoro-2-butene, and 4-hexafluoro-2-butene. 4. The method according to any one of claims 1 to 3,
Wherein the halogenated hydrocarbon is isopropyl chloride. 5. The method according to any one of claims 1 to 4,
A phenolic resin foam further containing a hydrocarbon having 6 or less carbon atoms. 6. The method of claim 5,
Wherein the content of the at least one member selected from the group consisting of chlorinated hydrofluoroolefins, chlorinated hydrofluoroolefins, non-chlorinated hydrofluoroolefins and halogenated hydrocarbons is at least one selected from the group consisting of the chlorinated hydrofluoroolefins, the non-chlorinated hydrofluoroolefins, the halogenated hydrocarbons, Is not less than 30% by mass based on the total amount of hydrocarbons of 6 or less. 7. The method according to any one of claims 1 to 6,
A phenolic resin foam further comprising a nitrogen-containing compound. 8. The method of claim 7,
Wherein the nitrogen-containing compound is a compound selected from the group consisting of urea, melamine, nuclidine, pyridine, hexamethylene tetramine, and mixtures thereof. 9. The method according to any one of claims 1 to 8,
Wherein the absolute value of the dimensional change after 3 cycles of dry and wet repetition is 2.0 mm or less. 10. The method according to any one of claims 1 to 9,
A phenolic resin foam obtained in accordance with JIS A 9511 (2003) 5.1.4 and having a brittleness of 50% or less. A phenolic resin foam laminate having a face material on the first and second faces of the phenolic resin foam according to any one of claims 1 to 10,
Wherein the face plate has gas permeability. A phenol resin, a surfactant, a curing catalyst, and a phenol resin for foaming and curing a foamable phenol resin composition containing at least one selected from the group consisting of chlorinated hydrofluoroolefin, non-chlorinated hydrofluoroolefin and halogenated hydrocarbon As a method for producing a resin foam,
The weight average molecular weight Mw of the phenolic resin obtained by gel permeation chromatography is 400 or more and 3000 or less,
Wherein the viscosity of the phenolic resin at 40 占 폚 is 1000 mPa 占 퐏 or more and 100000 mPa 占 퐏 or less,
The method for producing a phenolic resin foam according to claim 1, wherein the phenolic resin has a viscosity rising rate constant of 0.05 (1 / min) to 0.5 (1 / min) or less. 13. The method of claim 12,
Wherein the phenol resin has a loss tangent tan? At 40 占 폚 of 0.5 or more and 40.0 or less and a loss tangent tan? At 60 占 폚 of 2.0 or more and 90.0 or less.